Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3719—Polyamides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/28—Preparatory processes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/88—Polyamides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
  • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/10—General cosmetic use

Definitions

• the present invention relates to a specific polyamide polymer which is obtainable by two specific processes according to the invention.
• the invention further relates to the use of this polyamide polymer as a functional additive and to detergent compositions, cosmetic compositions, cleaning compositions and adhesive compositions comprising this polyamide polymer.
• Polymers which can be employed as functional additives e.g., in adhesive compositions, detergent compositions, cosmetic compositions or cleaning compositions are known in the art. Due to the increasing awareness of environmental issues, there exists a need for environmentally friendly, bio-based polymers.
• the international patent publications WO 2015/164598 A1 , WO 2015/164601 A1 , WO 2016/040962 A1 and WO 98/22478 A1 disclose such polymers, namely polyimide polymers and pyrrolidinone polymers, respectively.
• polymers based on itaconic acid which are water soluble over a broad pH-value range and have a number average molecular weight (M n ) of 1.000 to 10.000 g/mol are advantageous.
• M n number average molecular weight
• Those polymers - if used as functional additives - have a good stability against other chemicals and different environmental conditions, such as light, heat, exposure to air, especially compared to polymers comprising imide and lactam structures. Therefore, it was an object of the present invention to provide further polymers based on itaconic acid which are comparably environmentally friendly and sufficiently stable, while retaining good water solubility.
• polyamide polymers of the present invention This object is met by the polyamide polymers of the present invention.
• the inventors of the present invention have developed two specific processes which result in polyamide polymers according to the present invention. With these processes, pure polyamide polymers can be obtained which do not comprise lactam or pyrrolidinone structures. It has been surprisingly found that, when the polyamide polymers according to the present invention are employed as functional additives in the above-mentioned compositions, they can boost the performance of the respective compositions. For example, they boost the performance of moisture curing adhesives and sealants (especially based on polyurethane or silane-modified polymers), in particular with respect to concrete surface bonding. Further, they improve the washing performance of detergent and cleaning compositions, especially with regard to removing stains. They are also superior in their health and safety characteristics compared to monomeric functional additives, for example standard chelating agents like EDTA, and it is possible to use them in highly compacted laundry detergents.
• monomeric functional additives for example standard chelating agents like
• the processes disclosed herein are furthermore advantageous in that they do not employ a catalyst and are thus more cost efficient. Additionally, one of the synthesis methods does not employ any solvents and thus provides the polyamide polymer in a more cost-, time- and labour-efficient manner. Consequently, the process that does not use additional solvent according to the present invention is preferred.
• the invention thus relates to a process for the manufacture of a polyamide polymer, wherein itaconic acid or dimethyl itaconate is reacted with di- and/or triamine, comprising the steps:
• the number average molecular weight of the compounds according to formula I does not exceed 2000 g/mol; preferably the number average molecular weight of the compounds according to formula II does not exceed 440 g/mol; and preferably the number average molecular weight of the compounds according to formula III does not exceed 5000 g/mol.
• Compounds according to formulae I, II, or III are commercially available under the trade name Jeffamine® from Huntsman Corporation. x, y, and z in the ether amine compounds according to formulae I, II, or III may be integers or fractional numbers.
• ethylene diamine and diamine compounds of formula I and mixtures of diamine compounds of formula I with triamines of formula II and/or formula III; in those mixtures the molar content of diamine compounds of formula I preferably is above 50 %.
• the itaconic acid or dimethyl itaconate is added portion-wise to the reaction vessel, preferably in portions of equal weight, more preferably the individual portions are 1/2, 1/3, 1/4, 1/5, 1/6, 1/7 of the total weight of itaconic acid or dimethyl itaconate to be added.
• step ii) may be started with the addition of the itaconic acid or dimethyl itaconate or may be started once the complete amount has been added.
• the mixture in step ii) is heated to a temperature between 100°C and ⁇ 160°C, preferably to at least 120°C, more preferably to at least 130°C, most preferably to about 140°C, in particular with a rate of 1°C/min, preferably 2.5°C/min, more preferably 3°C/min, most preferably 4°C/min.
• step iii) may, in a further step iii), be heated to a temperature of 160°C or more, preferably at least 170 °C, more preferably at least 175°C, most preferably to about 185°C for 3 to 6 hours, preferably for 4 to 5.5 hours, more preferably for 4.5 to 5 hours.
• step a-ii) or step a-iii) vacuum is applied, preferably stepwise, to the reaction mixture until a pressure of >800 mbar, preferably 800 to 1 mbar is reached.
• the invention relates to a process for the manufacture of a polyamide polymer, wherein itaconic acid or dimethyl itaconate is reacted with the di- or triamine defined above, for example in air or preferably under an inert atmosphere, more preferably under nitrogen, comprising the steps:
• the invention also relates to a polyamide polymer obtained or obtainable according to a process of the invention, wherein the polyamide polymer preferably has a weight average molecular weight (M w ) of 1,000 to 10,000 g/mol, preferably 2,500 to 5,000 g/mol, as measured via gel permeation chromatography (GPC) using polystyrene standards and a mixture of an aqueous solution of 0.07 M Disodiumhydrogenphosphate (90 vol-%) and acetonitrile (10 vol-%) as elution agent.
• M w weight average molecular weight
• an aqueous solution of 25 wt.-% of the polyamide polymer in water has a pH-value of 4 to 7, preferably 4 to 5, more preferably 4.3 to 4.6, especially if the molar ratio of amine groups from the di- and/or triamine to carboxy groups from the itaconic acid or dimethyl itaconate in the preparation of the polyamide was below 1:1.
• an aqueous solution of 25 wt.-% of the polyamide polymer in water, based on the total weight of the aqueous solution, has a pH-value of 6 to 12, preferably 6 to 8, especially if said molar ratio in the preparation of the polyamide was above 1:1.
• the polyamide polymer according to the invention does not contain lactam, pyrrolidinone or polyimide groups. Preparing the polyamide polymer by process for the manufacture according to the invention assures that it will not contain such groups.
• the invention encompasses the use of the polyamide polymer according to the invention as a functional additive, preferably as enzyme activity booster and/or chelating agent for detergent compositions, cosmetic compositions, adhesive composition and/or cleaning compositions, more preferably for improving the cleaning performance of detergent compositions, cosmetic compositions and cleaning compositions or as an adhesion promoter or filler material in adhesive compositions. Also within the scope of the invention are the respective detergent, cosmetic, cleaning and adhesive compositions that comprise the polymers of the invention.
• Detergent composition comprising the polyamide polymer according to the invention, preferably contain the polymer in an amount of 0.1 to 10 wt.-%, more preferably 0.5 to 5 wt.-%, even more preferred 0.8 to 3 wt.-%, most preferred 1 to 1.5 wt.-%, based on the total weight of the detergent composition.
• Cosmetic compositions comprising the polyamide polymer according to the invention, contain the polymer preferably in an amount of 0.1 to 10 wt.-%, more preferably 1 to 5 wt.-%, even more preferred 1 to 3 wt.-%, most preferred 1 to 1.5 wt.-%, based on the total weight of the cosmetic composition.
• Cleaning compositions comprising the polyamide polymer according to the invention contain the polymer preferably in an amount of 0.1 to 10 wt.-%, more preferably 1 to 5 wt.-%, even more preferred 1 to 3 wt.-%, most preferred 1 to 1.5 wt.-%, based on the total weight of the cleaning composition.
• Adhesive compositions comprising the polyamide polymer according to the invention preferably contain the polymer in an amount of 0.1 to 80 wt.-%, more preferably 5 to 70 wt.-%, even more preferred 10 to 60 wt.-%, most preferred 15 to 50 wt.-%, based on the total weight of the adhesive composition.
• While the processes of the present invention are essentially based on the reaction of itaconic acid or dimethyl itaconate with di- and/or triamine, it should be self-evident that traces of other compounds can be present. However, in a preferred process of the invention, less than 1 wt.-%, preferably less than 0.1 wt.-%, more preferably 0.001 wt.-%, most preferably none monomers other than itaconic acid or dimethyl itaconate and di- and/or triamine are present, based on the total weight of the composition. In a further preferred process of the present invention no catalyst is employed.
• the precipitate/product is allowed to cool or actively cooled and the final product can preferably be taken out of the reaction vessel starting at a temperature of 130°C or less, preferably 100°C or less, more preferably 70°C or less, most preferably 50°C or less.
• the pressure can be reduced stepwise or continuously.
• the skilled person in the field knows which approach is most suitable given the circumstances.
• the polyamide polymer is acid-terminated and in a 25 wt.-% aqueous solution exhibits a pH-value of 3 to 7, more preferred 3.5 to 5, most preferred 4 to 4.8.
• the polyamide polymer is amine terminated and exhibits as a 25 wt.-% aqueous solution a pH-value of 7.5 to 12, more preferably 8.5 to 11, most preferably 9 to 10.5.
• water soluble polyamide polymers are water soluble.
• water soluble means that the solubility at 20°C in pure water of pH 7 is at least 50 g/L, preferably above 100 g/L, most preferably above 300 g/L, and may for example be as high as or even above 500 g/L, 600 g/L, 700 g/L or 750 g/l. Solubility may for example be measured according to the OECD Guidelines for the Testing of Chemicals, Section 1, Test No. 105: Water Solubility; adopted by the Council on 27th July 1995.
• the obtained polymer has a number average molecular weight (M n ) of 500 to 4,000 g/mol, preferably 1,000 to 3,000 g/mol, measured as an aqueous solution via GPC and polystyrene standards.
• M n number average molecular weight
• the obtained polymer has a polydispersity index of 1.5 to 2.5, preferably 1.7 to 2.1, more preferably 1.8 to 2.0, most preferably 1.9.
• compositions of the invention including the polyamide polymers disclosed herein, i.e., the detergent, cosmetic, cleaning or adhesive composition may comprise further components typical for such compositions. Accordingly, the additional components of said compositions are not particularly limited as long as the components do not negatively interact with the polyamide polymer, e.g., undergo a chemical reaction and precipitate, with the exception of adhesive compositions where a reaction with further components may be desired. In a preferred embodiment, all of the foregoing compositions are aqueous compositions. In preferred embodiments the detergent, cosmetic and cleaning compositions further comprise at least one surfactant and/or perfume.
• the adhesive composition is a moisture-curing reactive one component (1 K) or two component (2K) adhesive, based on polyurethane with isocyanate termination or a sealant based on a silane-modified polymer.
• Example 1 Polymer synthesis according to the invention, itaconic acid/ethylene diamine, molar ratio 1.01:1, no solvent.
• Example 2 Polymer synthesis according to the invention, itaconic acid/polyether amine (Jeffamine® D-230), molar ratio 1:1, no solvent.
• the mixture was heated to 170°C under nitrogen flow and the reflux condenser was replaced by a distillation column. Starting from reaching the set temperature of 170°C the reaction occurred for about 3h to achieve total conversion. Afterwards, the final product was discharged from the flask.
• the final obtained polyamide polymer is a yellowish-orange and tacky as well as hygroscopic solid at room temperature.
• the polyamide structure was confirmed via FT-IR spectroscopy showing typical vibration modes at 1661 cm- 1 (Amide I) and 1538 cm- 1 (Amide II) as well as the absence of any imide or lactam modes. Proton NMR (in DMSO) confirmed the obtained structure due to an amide peak around 7.85 ppm and the absence of any double bond peaks around 5 to 7.5 ppm.
• Example 3 Polymer synthesis according to the invention, itaconic acid/polyether amine (Jeffamine® ED-900), molar ratio 1:1, no solvent.
• the final obtained polyamide polymer is a yellowish-orange and tacky as well as hygroscopic solid at room temperature.
• the polyamide structure was confirmed via FT-IR spectroscopy showing typical vibration modes at 1667 cm- 1 (Amide I) and 1539 cm- 1 (Amide II) as well as the absence of any imide or lactam modes.
• Proton NMR (in DMSO) confirmed the obtained structure due to an amide peak around 7.80 ppm and the absence of any double bond peaks around 5 to 7.5 ppm.
• Example 4 Polymer synthesis according to the invention, itaconic acid/ethylene diamine, molar ratio 1:1, with Methanol (MeOH) as solvent.
• the solid precipitate was kept at 60°C under vacuum (stepwise from 300 to 100 mbar) for two hours before it was slowly heated (3°C/min) to 220°C stepwise under vacuum reduction (600 mbar to 45 mbar). At 220°C the mixture was kept for 2 hours at 45 mbar. Afterwards, the reaction was cooled to 130°C and the final product could be discharged from the flask. The final polyamide polymer was brittle, yellowish to brownish, and hygroscopic. The polyamide structure was confirmed via FT-IR spectroscopy showing typical vibration modes at 1648 cm- 1 (Amide I) and 1542 cm- 1 (Amide II) as well as the absence of any imide or lactam modes.
• Proton NMR (in DMSO) confirmed the obtained structure due to an amide peak around 8.05 ppm and the absence of any double bond peaks around 5 to 7.5 ppm.
• a pH value of 4.5 was obtained indicating acid terminated polymers without any remaining primary amine groups.
• Example 5 Polymer synthesis according to the invention, dimethyl itaconate/ethylene diamine, molar ratio 1:1, with MeOH as solvent.
• the mixture was kept for 1 hour at 40 mbar. Afterwards, the reaction was cooled to 130°C and the final product could be discharged from the flask.
• the final polyamide polymer was brittle, yellowish to brownish, and hygroscopic.
• the polyamide structure was confirmed via FT-IR spectroscopy showing typical vibration modes at 1652 cm -1 (Amide I) and 1540 cm -1 (Amide II) as well as the absence of any imide or lactam modes.
• Proton NMR (in DMSO) confirmed the obtained structure due to an amide peak around 8.05 ppm and the absence of any double bond peaks around 5 to 7.5 ppm.
• Comparative Example 6 Polymer synthesis not according to the invention, itaconic acid / hexamethylene diamine, molar ratio 1:1.
• the polyamide structure was confirmed via FT-IR spectroscopy showing typical vibration modes at 1650 cm- 1 (Amide I) and 154 cm -1 (Amide II) as well as the absence of any imide or lactam modes.
• Proton NMR (in DMSO) confirmed the obtained structure due to an amide peak around 8.05 ppm and the absence of any double bond peaks around 5 to 7.5 ppm.
• the polyamide polymer is insoluble in water and thus not suitable according to the present invention.
• Comparative Examples 7 to 10 Polymer synthesis not according to the invention, itaconic acid / hexamethylene diamine or ethylene diamine, molar ratio 2:1.
• Comparative examples 7 to 10 were performed according to examples 1 to 3 and comparative example 4, respectively, with the exception that in both cases itaconic acid was used in excess (molar ratio itaconic acid to ethylene diamine / hexamethylene diamine 2:1
• a mixture of imide and lactam structures were obtained as confirmed by the absence of any amide II vibration around 1510 to 1550 cm -1 within the IR spectra as well as the presence of imide and lactam modes between 1700 and 1720 cm -1 .
• Proton NMR analyses confirmed the presence of imide structures due to proton NMR (DMSO) signals around 5.6, 6.05, 6.48 and 1.9 ppm as well as lactam structures due to signals at 2.4, 3.25 and 12.6. Furthermore, proton NMR didn't show any amide peak at about 8 ppm.
• Example 11 and Comparative example 12 Washing performance tests
• liquid laundry detergent (comparative example 10) was added 1.5 wt.-%, based on the total weight of the total composition of the polyamide polymer obtained according to example 1 (example 9).
• the liquid laundry detergent contained inter alia acids, anionic and non-ionic surfactants, perfume, colouring agent and enzymes.
• the washing test was performed on several stains in a common washing machine (Miele W1514) at 40°C, cotton program, 1200 rpm, tab water, 66 mL of the liquid laundry detergents, respectively, and 3.5 kg of laundry.
• the whiteness i.e. the brightening of the sheets containing the stains, was determined photometrically as an indication of wash performance.
• a Minolta CM508d spectrometer device was used, which was calibrated beforehand using a white standard provided with the unit. In the following the type of stains are listed where a significant improvement could be obtained with the composition according to example 9 in comparison to the composition of comparative example 10.

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• 2017
  • 2017-07-25 EP EP17182956.7A patent/EP3434714A1/de active Pending
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